CN106450496A - High-capacity lithium ion secondary battery preparation method - Google Patents
High-capacity lithium ion secondary battery preparation method Download PDFInfo
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- CN106450496A CN106450496A CN201611062252.2A CN201611062252A CN106450496A CN 106450496 A CN106450496 A CN 106450496A CN 201611062252 A CN201611062252 A CN 201611062252A CN 106450496 A CN106450496 A CN 106450496A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Secondary Cells (AREA)
Abstract
The invention discloses a high-capacity lithium ion secondary battery preparation method which includes the steps: preparing a positive plate; preparing a negative plate: firstly, polishing a cobalt plate with abrasive paper, cleaning and drying the cobalt plate, placing the cleaned and dried cobalt plate on a laser processor base station, secondly, focusing high-energy-density focusing pulse laser beams on the surface of the cleaned cobalt plate in oxygen-containing atmosphere, and finally, scanning the surface of the cobalt plate by the laser beams at a uniform speed to prepare a CoO/Co composite material serving as the negative plate of a lithium ion secondary battery; assembly: sequentially winding the positive plate, a diaphragm and the negative plate to form a core, placing the core in a battery case, adding electrolyte into the battery case and then sealing the battery case to prepare the high-capacity lithium ion secondary battery. The prepared lithium ion secondary battery is high in capacity and power density, good in stability and excellent in safety.
Description
Technical field：
The present invention relates to field of batteries, it is specifically related to a kind of preparation method of high-capacity lithium-ion secondary cell.
Background technology：
With the arrival of information age, from the point of view of new energy technology development and application, particularly notebook computer, mobile electricity
The developing rapidly of the electronics and information industries such as words, digital camera, and the development of Aero-Space and Military Electronic Equipment, to movement
The requirement of power supply energy density and cycle performance also more and more higher, promotes the development of high power capacity secondary electrochemical power source.At present
The secondary cell using mainly has lead-acid battery, nickel-cadmium cell, Ni-MH battery and lithium ion battery.With people's environmental consciousness
Strengthen, the use of the toxic metals such as lead, cadmium is increasingly subject to limit, and develops the rechargeable type high energy environmental protection battery of a new generation
Become urgent task.
Lithium ion battery is accompanied by the secondary cell of new generation that lithium metal secondary battery grows up, and has open-circuit voltage
High, energy density is big, long service life, memory-less effect, the advantages of pollution-free and self-discharge rate is little.Since 90 years 20th century
Since first commercialization, development is very rapid, has been widely used in all kinds of portable electric appts, has been also the reason of electric automobile
Think one of energy.Lithium ion battery develops to the direction of high-performance (i.e. high-energy-density, long-life, safety), low cost,
Develop there is independent intellectual property right be applied to high-performance novel battery material and technology, not only there is good economy and society
Meeting benefit, with more important strategic importance.Now commercially use lithium ion battery substantially adopts material with carbon element as negative
, as positive electrode, electrolyte is using the organic solvent containing lithium salts, but improves further for pole material and high potential lithium intercalation compound
Specific capacity and first charge-discharge efficiency, reduces cost and raising safety will be the focuses studied.Wherein develop new Gao Rong
Amount, long-life both positive and negative polarity intercalation materials of li ions are the key points improving performance of lithium ion battery.
Content of the invention：
It is an object of the invention to provide a kind of preparation method of high-capacity lithium ion cell, this short preparation period, efficiency high,
Prepared lithium ion secondary battery capacity is big, and specific power is high, and charge-discharge performance is good, safety, excellent in stability.
For achieving the above object, the present invention employs the following technical solutions：
A kind of preparation method of high-capacity lithium-ion secondary cell, comprises the following steps：
(1) preparation of positive plate：
Positive active material, conductive agent, binding agent are dissolved in N-Methyl pyrrolidone, are not higher than in vacuum
0.08MPa, stirs 10-20h in the state of 1000 revs/min, obtains mixed slurry, by mixed slurry under the power of 1000W
Ultrasonic 10-15h, crosses 100 eye mesh screens after ultrasonic end, obtains anode sizing agent；The anode sizing agent being obtained is coated positive pole current collections
Body surface face, and be thermally dried, obtain positive plate；
(2) preparation of negative plate：
First cobalt plate is polished with sand paper, be placed in after cleaning-drying on laser processor base station, then that focused high-energy is close
Degree pulse laser beam focus on cleaning in oxygen-containing atmosphere after cobalt plate surface, finally by laser beam with uniform speed to cobalt plate
Surface is scanned processing, prepared CoO/Co composite, and it is as the negative plate of lithium rechargeable battery；
(3) assemble：
Positive plate, barrier film, negative plate are wound formation pole piece successively, pole piece is placed in battery case, and in battery case
Add electrolyte, then seal, prepared high-capacity lithium-ion secondary cell.
Preferred as technique scheme, in step (1), described positive active material is nickle cobalt lithium manganate.
Preferred as technique scheme, in step (1), described conductive agent is electrically conductive graphite, CNT, acetylene black
One of.
Preferred as technique scheme, in step (1), described binding agent is HPAM Degraded Bacteria, gathers inclined difluoro
One of ethylene, butadiene-styrene rubber, tetrafluoraoethylene-hexafluoropropylene copolymer, polyphenylene sulfide, epoxy resin.
Preferred as technique scheme, in step (1), described positive electrode collector is aluminium foil.
Preferred as technique scheme, in step (2), described focused high-energy-density pulse laser is femtosecond, psec
Or nanosecond type, optical maser wavelength is ultraviolet light, visible or infrared light, and laser frequency is 1KHZ-10MHZ, and pulsed laser energy is
0.01 μ J-1mJ, laser scanning speed is 0.1mm/s-10m/s, and spacing is 0.001-2mm.
Preferred as technique scheme, in step (2), described oxygen-containing atmosphere is air atmosphere.
Preferred as technique scheme, in step (2), prepared CoO/Co composite, CoO is by 3-5nm
Individual particle is deposited in the micron particles composition with porous property of cobalt plate surface at random
Preferred as technique scheme, in step (3), described barrier film is polyimide porous film, its porosity
For 35-70%, average pore diameter is 30-60nm.
Preferred as technique scheme, in step (3), described electrolyte is dimethyl carbonate, diethyl carbonate, carbon
Vinyl acetate, the mixture of lithium hexafluoro phosphate or dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, the mixing of lithium hexafluoro phosphate
Thing or dimethyl carbonate, diethyl carbonate, ethyl n-butyrate., the mixture of lithium hexafluoro phosphate or dimethyl carbonate, diethyl carbonate,
Allyl carbonate, the mixture of lithium hexafluoro phosphate.
The invention has the advantages that：
The present invention adopts the method for laser ablation CoO/Co composite to be obtained as the negative plate of lithium rechargeable battery,
Its specific capacity is big, and prepared nano Co O is directly grown in cobalt plate, is firmly combined with, good stability；
The present invention selects suitable positive electrode, barrier film and electrolyte, prepared lithium rechargeable battery stable circulation
Property good, there is higher capacity, power density is big, have a safety feature.
Specific embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
Release the present invention, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of high-capacity lithium-ion secondary cell, comprises the following steps：
(1) preparation of positive plate：
Nickle cobalt lithium manganate, electrically conductive graphite, HPAM Degraded Bacteria are dissolved in N-Methyl pyrrolidone, not high in vacuum
In 0.08MPa, stir 10h in the state of 1000 revs/min, obtain mixed slurry, mixed slurry is super under the power of 1000W
Sound 10h, crosses 100 eye mesh screens after ultrasonic end, obtains anode sizing agent；The anode sizing agent being obtained is coated positive pole current collections body surface
Face, and be thermally dried, obtain positive plate；
(2) preparation of negative plate：
First cobalt plate is polished with sand paper, be placed in after cleaning-drying on laser processor base station, then that focused high-energy is close
Degree pulse laser beam focus on cleaning in air atmosphere after cobalt plate surface, finally by laser beam with uniform speed to cobalt plate
Surface is scanned processing, prepared CoO/Co composite, and it is as the negative plate of lithium rechargeable battery；Wherein, focus on height
Can density pulse laser be femtosecond, psec or nanosecond type, optical maser wavelength is ultraviolet light, visible or infrared light, and laser frequency is
1KHZ-10MHZ, pulsed laser energy is 0.01 μ J-1mJ, and laser scanning speed is 3mm/s, and spacing is 0.001-2mm；
(3) assemble：
Positive plate, polyimide porous film, negative plate are wound formation pole piece successively, pole piece are placed in battery case,
And add electrolyte in battery case, then seal, prepared high-capacity lithium-ion secondary cell；Wherein, polyimide foraminous are thin
The porosity of film is 35%, and average pore diameter is 30nm；Electrolyte be dimethyl carbonate, diethyl carbonate, ethylene carbonate, six
The mixture of lithium fluophosphate.
Embodiment 2
A kind of preparation method of high-capacity lithium-ion secondary cell, comprises the following steps：
(1) preparation of positive plate：
Nickle cobalt lithium manganate, CNT, polyvinylidene fluoride are dissolved in N-Methyl pyrrolidone, are not higher than in vacuum
0.08MPa, stirs 20h in the state of 1000 revs/min, obtains mixed slurry, and mixed slurry is ultrasonic under the power of 1000W
15h, crosses 100 eye mesh screens after ultrasonic end, obtains anode sizing agent；The anode sizing agent being obtained is coated positive electrode collector surface,
And be thermally dried, obtain positive plate；
(2) preparation of negative plate：
First cobalt plate is polished with sand paper, be placed in after cleaning-drying on laser processor base station, then that focused high-energy is close
Degree pulse laser beam focus on cleaning in air atmosphere after cobalt plate surface, finally by laser beam with uniform speed to cobalt plate
Surface is scanned processing, prepared CoO/Co composite, and it is as the negative plate of lithium rechargeable battery；Wherein, focus on height
Can density pulse laser be femtosecond, psec or nanosecond type, optical maser wavelength is ultraviolet light, visible or infrared light, and laser frequency is
1KHZ-10MHZ, pulsed laser energy is 0.01 μ J-1mJ, and laser scanning speed is 3cm/s, and spacing is 0.001-2mm；
(3) assemble：
Positive plate, polyimide porous film, negative plate are wound formation pole piece successively, pole piece are placed in battery case,
And add electrolyte in battery case, then seal, prepared high-capacity lithium-ion secondary cell；Wherein, polyimide foraminous are thin
The porosity of film is 70%, and average pore diameter is 60nm；Electrolyte be dimethyl carbonate, diethyl carbonate, gamma-butyrolacton, six
The mixture of lithium fluophosphate.
Embodiment 3
A kind of preparation method of high-capacity lithium-ion secondary cell, comprises the following steps：
(1) preparation of positive plate：
Nickle cobalt lithium manganate, acetylene black, butadiene-styrene rubber are dissolved in N-Methyl pyrrolidone, are not higher than in vacuum
0.08MPa, stirs 13h in the state of 1000 revs/min, obtains mixed slurry, and mixed slurry is ultrasonic under the power of 1000W
11h, crosses 100 eye mesh screens after ultrasonic end, obtains anode sizing agent；The anode sizing agent being obtained is coated positive electrode collector surface,
And be thermally dried, obtain positive plate；
(2) preparation of negative plate：
First cobalt plate is polished with sand paper, be placed in after cleaning-drying on laser processor base station, then that focused high-energy is close
Degree pulse laser beam focus on cleaning in air atmosphere after cobalt plate surface, finally by laser beam with uniform speed to cobalt plate
Surface is scanned processing, prepared CoO/Co composite, and it is as the negative plate of lithium rechargeable battery；Wherein, focus on height
Can density pulse laser be femtosecond, psec or nanosecond type, optical maser wavelength is ultraviolet light, visible or infrared light, and laser frequency is
1KHZ-10MHZ, pulsed laser energy is 0.01 μ J-1mJ, and laser scanning speed is 3dm/s, and spacing is 0.001-2mm；
(3) assemble：
Positive plate, polyimide porous film, negative plate are wound formation pole piece successively, pole piece are placed in battery case,
And add electrolyte in battery case, then seal, prepared high-capacity lithium-ion secondary cell；Wherein, polyimide foraminous are thin
The porosity of film is 45%, and average pore diameter is 40nm；Electrolyte is dimethyl carbonate, diethyl carbonate, ethyl n-butyrate., hexafluoro
The mixture of lithium phosphate.
Embodiment 4
A kind of preparation method of high-capacity lithium-ion secondary cell, comprises the following steps：
(1) preparation of positive plate：
Nickle cobalt lithium manganate, electrically conductive graphite, tetrafluoraoethylene-hexafluoropropylene copolymer are dissolved in N-Methyl pyrrolidone,
Vacuum is not higher than 0.08MPa, stirs 16h, obtain mixed slurry, by mixed slurry in 1000W in the state of 1000 revs/min
Power under ultrasonic 12h, after ultrasonic end cross 100 eye mesh screens, obtain anode sizing agent；The anode sizing agent being obtained is coated positive pole
Collector surface, and be thermally dried, obtain positive plate；
(2) preparation of negative plate：
First cobalt plate is polished with sand paper, be placed in after cleaning-drying on laser processor base station, then that focused high-energy is close
Degree pulse laser beam focus on cleaning in air atmosphere after cobalt plate surface, finally by laser beam with uniform speed to cobalt plate
Surface is scanned processing, prepared CoO/Co composite, and it is as the negative plate of lithium rechargeable battery；Wherein, focus on height
Can density pulse laser be femtosecond, psec or nanosecond type, optical maser wavelength is ultraviolet light, visible or infrared light, and laser frequency is
1KHZ-10MHZ, pulsed laser energy is 0.01 μ J-1mJ, and laser scanning speed is 3m/s, and spacing is 0.001-2mm；
(3) assemble：
Positive plate, polyimide porous film, negative plate are wound formation pole piece successively, pole piece are placed in battery case,
And add electrolyte in battery case, then seal, prepared high-capacity lithium-ion secondary cell；Wherein, polyimide foraminous are thin
The porosity of film is 55%, and average pore diameter is 50nm；Electrolyte be dimethyl carbonate, diethyl carbonate, Allyl carbonate, six
The mixture of lithium fluophosphate.
Embodiment 5
A kind of preparation method of high-capacity lithium-ion secondary cell, comprises the following steps：
(1) preparation of positive plate：
Nickle cobalt lithium manganate, CNT, polyphenylene sulfide are dissolved in N-Methyl pyrrolidone, are not higher than in vacuum
0.08MPa, stirs 18h in the state of 1000 revs/min, obtains mixed slurry, and mixed slurry is ultrasonic under the power of 1000W
13h, crosses 100 eye mesh screens after ultrasonic end, obtains anode sizing agent；The anode sizing agent being obtained is coated positive electrode collector surface,
And be thermally dried, obtain positive plate；
(2) preparation of negative plate：
First cobalt plate is polished with sand paper, be placed in after cleaning-drying on laser processor base station, then that focused high-energy is close
Degree pulse laser beam focus on cleaning in air atmosphere after cobalt plate surface, finally by laser beam with uniform speed to cobalt plate
Surface is scanned processing, prepared CoO/Co composite, and it is as the negative plate of lithium rechargeable battery；Wherein, focus on height
Can density pulse laser be femtosecond, psec or nanosecond type, optical maser wavelength is ultraviolet light, visible or infrared light, and laser frequency is
1KHZ-10MHZ, pulsed laser energy is 0.01 μ J-1mJ, and laser scanning speed is 7m/s, and spacing is 0.001-2mm；
(3) assemble：
Positive plate, polyimide porous film, negative plate are wound formation pole piece successively, pole piece are placed in battery case,
And add electrolyte in battery case, then seal, prepared high-capacity lithium-ion secondary cell；Wherein, polyimide foraminous are thin
The porosity of film is 65%, and average pore diameter is 55nm；Electrolyte be dimethyl carbonate, diethyl carbonate, ethylene carbonate, six
The mixture of lithium fluophosphate.
The lithium rechargeable battery that embodiment 1-5 is obtained carries out 45 DEG C of cycle performance tests, and wherein charging current is
0.5C, discharge current is 0.5C, and the capability retention after its 2000 circulations is all more than 90%；
The lithium rechargeable battery that embodiment 1-5 is obtained carries out 10 DEG C of cycle performance tests, and wherein charging current is
0.5C, discharge current is 0.5C, and the capability retention after its 800 circulations is all more than 88%；
High-temperature lithium ion battery circulation and cold cycle excellent performance that the present invention described above is obtained.
Claims (10)
1. a kind of preparation method of high-capacity lithium-ion secondary cell is it is characterised in that comprise the following steps：
(1) preparation of positive plate：
Positive active material, conductive agent, binding agent are dissolved in N-Methyl pyrrolidone, are not higher than 0.08MPa in vacuum,
In the state of 1000 revs/min stir 10-20h, obtain mixed slurry, by mixed slurry under the power of 1000W ultrasonic 10-15h,
Cross 100 eye mesh screens after ultrasonic end, obtain anode sizing agent；The anode sizing agent being obtained is coated positive electrode collector surface, goes forward side by side
Row heat drying, obtains positive plate；
(2) preparation of negative plate：
First cobalt plate is polished with sand paper, be placed in after cleaning-drying on laser processor base station, then by focused high-energy-density arteries and veins
Laser beam focus on cleaning in oxygen-containing atmosphere after cobalt plate surface, finally by laser beam with uniform speed to cobalt plate surface
It is scanned processing, prepared CoO/Co composite, it is as the negative plate of lithium rechargeable battery；
(3) assemble：
Positive plate, barrier film, negative plate are wound formation pole piece successively, pole piece is placed in battery case, and add in battery case
Electrolyte, then seals, prepared high-capacity lithium-ion secondary cell.
2. as claimed in claim 1 a kind of preparation method of high-capacity lithium-ion secondary cell it is characterised in that：Step (1)
In, described positive active material is nickle cobalt lithium manganate.
3. as claimed in claim 1 a kind of preparation method of high-capacity lithium-ion secondary cell it is characterised in that：Step (1)
In, described conductive agent is one of electrically conductive graphite, CNT, acetylene black.
4. as claimed in claim 1 a kind of preparation method of high-capacity lithium-ion secondary cell it is characterised in that：Step (1)
In, described binding agent be HPAM Degraded Bacteria, polyvinylidene fluoride, butadiene-styrene rubber, tetrafluoraoethylene-hexafluoropropylene copolymer,
One of polyphenylene sulfide, epoxy resin.
5. as claimed in claim 1 a kind of preparation method of high-capacity lithium-ion secondary cell it is characterised in that：Step (1)
In, described positive electrode collector is aluminium foil.
6. as claimed in claim 1 a kind of preparation method of high-capacity lithium-ion secondary cell it is characterised in that：Step (2)
In, described focused high-energy-density pulse laser is femtosecond, psec or nanosecond type, and optical maser wavelength is ultraviolet light, visible ray or infrared
Light, laser frequency is 1KHZ-10MHZ, and pulsed laser energy is 0.01 μ J-1mJ, and laser scanning speed is 0.1mm/s-10m/s,
Spacing is 0.001-2mm.
7. as claimed in claim 1 a kind of preparation method of high-capacity lithium-ion secondary cell it is characterised in that：Step (2)
In, described oxygen-containing atmosphere is air atmosphere.
8. as claimed in claim 1 a kind of preparation method of high-capacity lithium-ion secondary cell it is characterised in that：Step (2)
In, prepared CoO/Co composite, CoO is that to be deposited in having of cobalt plate surface at random by the individual particle of 3-5nm many
The micron particles composition of porous
9. as claimed in claim 1 a kind of preparation method of high-capacity lithium-ion secondary cell it is characterised in that：Step (3)
In, described barrier film is polyimide porous film, and its porosity is 35-70%, and average pore diameter is 30-60nm.
10. as claimed in claim 1 a kind of preparation method of high-capacity lithium-ion secondary cell it is characterised in that：Step (3)
In, described electrolyte is dimethyl carbonate, diethyl carbonate, ethylene carbonate, the mixture of lithium hexafluoro phosphate or carbonic acid diformazan
Ester, diethyl carbonate, gamma-butyrolacton, the mixture of lithium hexafluoro phosphate or dimethyl carbonate, diethyl carbonate, ethyl n-butyrate., six
The mixture of lithium fluophosphate or dimethyl carbonate, diethyl carbonate, Allyl carbonate, the mixture of lithium hexafluoro phosphate.
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